Carbon–sulfur bond reductive coupling from a platinum(<scp>ii</scp>) thiolate complex

Niazi, Maryam; Shahsavari, Hamid R.; Haghighi, Mohsen Golbon; Halvagar, Mohammad Reza; Hatami, Samaneh; Notash, Behrouz

doi:10.1039/c6ra21756g

Cited by 19 publications

(27 citation statements)

References 77 publications

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“…Crystallographic data are collected in Table S1. The platinum center in 1 has a distorted square‐planar coordination geometry imposed by the ppy cyclometalated ligand . The Pt–P distance in the structure is 2.222(2) Å, in good agreement with the value reported for the PPh 3 analogue .…”

Section: Resultssupporting

confidence: 82%

“…The molecular structure reveals short C–H ··· π (3.245–3.436 Å; phenyl or pyridine rings of PPh 2 py) and C–H ··· Cl [2.609(5) Å] intramolecular interactions (i.e., the C–H group adjacent to the coordinated carbon and nitrogen atoms of the ppy ligand, respectively; see Figure S5). The intramolecular interactions can influence the high‐ (H 9 ) or low‐field (H 2 ) shift of these resonance signals in the 1 H NMR spectrum of 1 …”

Section: Resultsmentioning

confidence: 99%

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Cyclometalated Platinum(II) Complexes Comprising 2‐(Diphenylphosphino)pyridine and Various Thiolate Ligands: Synthesis, Spectroscopic Characterization, and Biological Activity

et al. 2017

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The known cyclometalated platinum(II) complex [Pt(ppy)(DMSO)(Cl)] (A) in which ppy = 2‐phenylpyridinate, was treated with 2‐(diphenylphosphino)pyridine (PPh2py, PN) (1 equiv.) and readily afforded complex [Pt(ppy)(PPh2py‐κ1P)(Cl)] (1). The transphobia effect (T) and single‐crystal X‐ray diffraction crystallography confirmed that the phosphine ligand in 1 is located trans to the nitrogen atom of the cyclometalating fragment (ppy). Compound 1 was treated with various thiolate reagents (1 equiv.) at room temperature, leading to the displacement of the chloride ligand in 1 by thiolate ligands through a salt metathesis reaction. The reaction led to the formation of a series of monomeric complexes with the general formula [Pt(ppy)(PPh2py‐κ1P)(SR)] (2a–2d), where SR = deprotonated form of pyridine‐2‐thiol (HSpy, 2a), pyrimidine‐2‐thiol (HSpyN, 2b), thiophenol (HSPh, 2c), and 2‐thiazoline‐2‐thiol (HSt, 2d). All complexes have been characterized by NMR spectroscopy. The biological activities of the complexes were evaluated against three human cancer cell lines, including A549 (human lung cancer), SKOV3 (human ovarian cancer), and MCF7 (human breast cancer), by means of the MTT assay [MTT = 3‐(4,5‐dimethylthiazol‐yl)‐2,5‐diphenyltetrazolium bromide]. Compounds 2a and 2b presented effective, potent cytotoxic activity regarding the cell lines. Electrophoretic mobility shift assays on plasmid DNA and molecular modeling investigations were also performed to determine the specific binding mode or the binding orientation of the complexes to DNA.

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Section: Resultssupporting

confidence: 82%

Section: Resultsmentioning

confidence: 99%

Cyclometalated Platinum(II) Complexes Comprising 2‐(Diphenylphosphino)pyridine and Various Thiolate Ligands: Synthesis, Spectroscopic Characterization, and Biological Activity

et al. 2017

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“…31 P{ 1 H} NMR spectra display a sharp singlet signal with platinum satellites at 22.2, 23.4 and 24.2 ppm, for complexes 1–3 , respectively, confirming the presence of Pt (II)‐bound PCy 3 ligands. The coupling constants of 1 J PtP = 2162 Hz ( 1 ), 1937 Hz ( 2 ) and 2052 Hz ( 3 ) are typical for the P‐ trans ‐C (sp 2 ) geometry . It is noteworthy that this significant difference in the coupling values of 1 J PtP (about 120 Hz), is attributed to the trans influence of coordinated carbon atom of the C^N‐cyclometalated ligands (Obpy > bzq > ppy) .…”

Section: Resultsmentioning

confidence: 91%

Carbon‐iodide bond activation by cyclometalated Pt (II) complexes bearing tricyclohexylphosphine ligand: A comparative kinetic study and theoretical elucidation

Chamyani

Shahsavari

Abedanzadeh

et al. 2018

Applied Organom Chemis

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Yield: 76%. Elem. anal. Calcd for C 30 H 44 NPPt (644.73); C, 55.89; H, 6.88; N, 2.17. Found: C, 55.76; H, 6.82; N, 2.26. 1 H NMR (400 MHz, CDCl 3 ): δ = 1.07 (d, 3 J PH = 5.3 Hz, 2 J PtH = 84.5 Hz, 3H, PtMe), 1.20-1.40 (m, 9H, Cy), 1.65 (m, 6H, Cy), 1.70-1.90 (m, 9H, Cy), 1.97-2.14 (m, 6H, Cy), 2.36 (m, 3H, Cy), 7.09 (m, 1H, H 4′ ), 7.16 (t, 1H, 3 J HH = 7.3 Hz, H 5′ ), 7.35 (td, 1H, 3 J HH = 7.3 Hz, 4 J HH = 2.9 Hz, 4 J PtH = 29.7 Hz, H 5 ), 7.70 (bd, 1H, 3 J HH = 7.8, H 4 ), 7.85 (m, 2H, H 3 and H 6′ ), 7.95 (dd, 1H, 3 J HH = 6.3 Hz, 4 J HH = 1.1 Hz, 3 J PtH = 46.8 Hz, H 3′ ), 8.84 (d, 1H, 3 J HH = 5.6 Hz, 3 J PtH = 18.3 Hz, H 6 ); 13 C{ 1 H} NMR (101 MHz, CDCl 3 ): δ = −15.3 (d, 2 Yield: 81%. Elem. anal. Calcd for C 32 H 44 NPPt (668.75); C, 57.47; H, 6.63; N, 2.09. Found: C, 57.31; H, 6.69; N, 2.21. 1 H NMR (400 MHz, CDCl 3 ): δ = 0.83-2.61 (3H of Me and 33H of Cy), 7.46 (dd, 1H, 3 J HH = 7.9 Hz, 3 J HH = 7.8 Hz, H 8 ), 7.56 (d, 1H, 3 J HH = 8.1 Hz, H 6 ), 7.67 (d, 1H, 3 J HH = 8.1 Hz, H 5 ), 7.74 (m, 1H, H 3 ), 7.82 (d, 1H, 3 J HH = 8.7 Hz, H 7 ), 8.23 (dd, 1H, 3 J HH = 7.1 Hz, 3 J PtH = 45.5 Hz, H 9 ), 8.34 (d, 1H, 3 J HH = 8.3 Hz, H 4 ), 9.15 (d, 1H, 3 J HH = 5.3 Hz, 4 J HH = 1.1 Hz, 3 J PtH = 17.2 Hz, H 2 ); 13 C{ 1 H} NMR (101 MHz, CDCl 3 ): δ = −16.0 (d, 2 J PC = 7 Hz, 1 J PtC = 754 Hz, PtMe), 26.6 (s, C of PCy 3 ), 1 H NMR (400 MHz) in CDCl 3 : δ = 0.86-2.11 (39H, aliphatic region, overlapping multiplets of 2Me and 3Cy), 7.21 (m, 1H, 3 J HH = 6.6 Hz, H 4′ ), 7.50 (dd, 2H, 3 J HH = 6.5 Hz, 4 J HH = 2.1 Hz, 4 J PtH = 53.1 Hz, H 5 and H 3′ ), 8.03 (m, 1H, 3 J HH = 7.9 Hz, 3 J HH = 7.8 Hz, H 4 ), 8.22 (d, 1H, 3 J HH = 6.5 Hz, H 5′ ), 10.09 (d, 3 J HH = 5.5 Hz, 4 J PtH = 16.1 Hz, 1H, H 3 ), 10.26 (d, 1H, 3 J HH = 7.83 Hz, 1H, H 6 ); 13 C{ 1 H} NMR (101 MHz, CDCl 3 ): δ = −7.3 (d, 2 J PC = 4 Hz, 1 J PtC = 624 Hz, PtMe (Me trans to N)), 10.7 (d, 2 J PC = 106 Hz, 1 J PtC = 461 Hz, PtMe (Me trans J PtP = 955 Hz, 1P of PCy 3 ); 195 Pt{ 1 H} NMR (86 MHz, CDCl 3 ): δ = −3215.1 (s, 1 J PtP = 957 Hz, 1Pt). 4.3.2 | cis-[PtMe 2 I(k 2 N,C-ppy)(PCy 3 )] (2a) 1 H NMR (400 MHz) in CDCl 3 : δ = 0.85-2.12 (39H, aliphatic region, overlapping multiplets of 2Me and 3Cy), 7.22 (dd, 3 J HH = 7.8 Hz, 3 J HH = 7.3 Hz, 1H, H 4′ ), 7.33 (m, 2H, H 5′ and H 6′ ), 7.50 (d, 2H, 3 J HH = 7.8 Hz, 4 J PtH = 48.9 Hz, H 3′ ), 7.71 (m, 1H, H 4 ), 7.87 (ddd, 3 J HH = 7.5 Hz, 3 J HH = 8.0 Hz, 4 J HH = 1.3 Hz, 1H, H 5 ), 7.96 (d, 1H, 3 J HH = 8.1 Hz, H 3 ), 10.12 (d, 1H, 3 J HH = 14.8 Hz, H 6 ); 13 C{ 1 H} NMR (101 MHz, CDCl 3 ): δ = −7.3 (d, 2 J PC = 3 Hz, 1 J PtC = 670 Hz, PtMe (Me trans to N)), 10.4 (d, 2 J PC = 109 Hz, 1 J PtC = 469 Hz, PtMe (Me trans to P)), 26.4 (s, C of PCy 3 ), 27.9 (d, 3 J PC = 10 Hz, C of

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“…Organic compounds containing a thiol group (RSH) or its corresponding anion form, called thiolate (RS − ), are chemically unique and can be used as a source of sulfur donor ligands . Several complexes based on thiolate ligands especially of the type L−Au(I)−SR have been prepared.…”

Section: Introductionmentioning

confidence: 99%

(Benzyl isocyanide)gold(I) pyrimidine‐2‐thiolate complex: Synthesis and biological activity

Fereidoonnezhad

Shahsavari

Lotfi

et al. 2018

Applied Organom Chemis

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The reaction of [(Me2S)AuCl] with an equimolar amount of benzyl isocyanide (PhCH2NC) ligand led to the formation of complex [(PhCH2NC)AuCl] (1). The solid‐state structure of 1 was determined using the X‐ray diffraction method. Through a salt metathesis reaction, the chloride ligand in 1 was replaced by pyrimidine‐2‐thiolate (SpyN−) to afford the complex [(PhCH2NC)Au(η1‐S‐Spy)] (2), which was characterized spectroscopically. The cytotoxic activities of 1 and 2 were evaluated against three human cancer cell lines: ovarian carcinoma (SKOV3), lung carcinoma (A549) and breast carcinoma (MCF‐7). Complex 2 showed higher cytotoxicity than cisplatin against SKOV3 and MCF‐7 cancer cell lines. It showed a strong anti‐proliferative activity with IC50 of 7.80, 6.26 and 6.14 μM, compared with that measured for cisplatin which was 7.62, 12.36 and 11.47 μM, against A549, SKOV3 and MCF‐7 cell lines, respectively. The induction of cellular apoptosis by 2 was also studied on MCF‐7 cell line. Our results indicated that 2 could induce apoptosis in cancerous cells in a dose‐dependent manner.

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Carbon–sulfur bond reductive coupling from a platinum(ii) thiolate complex

Abstract: Complex 1 was reacted with different alkyl halides at room temperature. This reaction proceeded via formation of binuclear intermediate complex 3 and through C–S bond reductive coupling to produce alkyl sulfides and corresponding halide complexes 2.

Cited by 19 publications

References 77 publications

Cyclometalated Platinum(II) Complexes Comprising 2‐(Diphenylphosphino)pyridine and Various Thiolate Ligands: Synthesis, Spectroscopic Characterization, and Biological Activity

Cyclometalated Platinum(II) Complexes Comprising 2‐(Diphenylphosphino)pyridine and Various Thiolate Ligands: Synthesis, Spectroscopic Characterization, and Biological Activity

Carbon‐iodide bond activation by cyclometalated Pt (II) complexes bearing tricyclohexylphosphine ligand: A comparative kinetic study and theoretical elucidation

(Benzyl isocyanide)gold(I) pyrimidine‐2‐thiolate complex: Synthesis and biological activity

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